EP2624066B1 - Ladungselement und verfahren zur herstellung davon - Google Patents

Ladungselement und verfahren zur herstellung davon Download PDF

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Publication number
EP2624066B1
EP2624066B1 EP11829330.7A EP11829330A EP2624066B1 EP 2624066 B1 EP2624066 B1 EP 2624066B1 EP 11829330 A EP11829330 A EP 11829330A EP 2624066 B1 EP2624066 B1 EP 2624066B1
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EP
European Patent Office
Prior art keywords
general formula
independently represent
condensate
surface layer
group
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EP11829330.7A
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English (en)
French (fr)
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EP2624066A1 (de
EP2624066A4 (de
Inventor
Noriaki Kuroda
Noriko SUZUMURA
Yuya Tomomizu
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Canon Inc
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Canon Inc
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Publication of EP2624066A1 publication Critical patent/EP2624066A1/de
Publication of EP2624066A4 publication Critical patent/EP2624066A4/de
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Publication of EP2624066B1 publication Critical patent/EP2624066B1/de
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G03G15/02—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices
    • G03G15/0208—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices by contact, friction or induction, e.g. liquid charging apparatus
    • G03G15/0216—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices by contact, friction or induction, e.g. liquid charging apparatus by bringing a charging member into contact with the member to be charged, e.g. roller, brush chargers
    • G03G15/0233—Structure, details of the charging member, e.g. chemical composition, surface properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/56—Boron-containing linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/58—Metal-containing linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G03G15/02—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices
    • G03G15/0258—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices provided with means for the maintenance of the charging apparatus, e.g. cleaning devices, ozone removing devices G03G15/0225, G03G15/0291 takes precedence
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness

Definitions

  • the present invention relates to a charging member used in electrophotographic apparatuses and a method for manufacturing the same.
  • electrographic members are used, and examples of the electrophotographic member includes a charging member for charging an outer surface of a photosensitive member by being into contact with the outer surface, a developing member for developing an electrostatic latent image formed on the outer surface of the photosensitive member to form a toner image and a cleaning member for removing toner attached to the photosensitive member.
  • a charging member having a supporting member and an elastic layer (conductive elastic layer) provided on the supporting member is generally employed in view of keeping a sufficient abutting nip with the photosensitive member.
  • a surface layer is generally provided to the surface of the elastic layer.
  • Patent literature 1 discloses a charging member having a surface layer, which is formed of polysiloxane having a fluoroalkyl group and an oxyalkylene group by a so-called sol-gel method.
  • a site of a fluoroalkyl group surface free energy is lowered.
  • a toner and external additives used in the toner are rarely adhered to the surface even if the member is repeatedly used for a long time.
  • the charging member if it is employed in a DC contact charging system, can be used as a charging member capable of stably charging and outputting images for a long time.
  • a method for suppressing adhesion of dirt to the surface of an electrographic member a method of appropriately roughening the surface of the surface layer by adding coarse particles to the surface layer is known, as described in Patent literature 2.
  • the present invention is directed to provide a charging member having an appropriately roughened surface without using coarse particles and capable of suppressing adhesion of dirt to the surface, and a method for manufacturing the same.
  • a charging member comprising a supporting member, an elastic layer and a surface layer, wherein the surface layer comprises a polymer compound having a Si-O-M bond; and the polymer compound has at least one structural unit selected from structural units represented by the following general formula (1) and the following general formula (2), and has a structural unit represented by the following general formula (3); and wherein the charging member has a crack extending from the surface thereof to the elastic layer; and the crack has convexly raised edge by which the surface thereof is roughened.
  • M represents an element selected from the group consisting of Ti, Zr and Hf.
  • General formula (2) MO 5/2 represents an element selected from the group consisting of Ti, Zr and Hf.
  • M represents an element Ta.
  • R 1 and R 2 each independently represent any one of the following general formulas (4) to (7).
  • R 3 to R 7 , R 10 to R 14 , R 19 , R 20 , R 25 and R 26 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a carboxyl group or an amino group
  • R 8 , R 9 , R 15 to R 18 , R 23 , R 24 and R 29 to R 32 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 21 , R 22 , R 27 and R 28 each independently represent a hydrogen atom, an alkoxyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms
  • n, m, l, q, s and t each independently represent an integer of 1 to 8
  • p and r each independently represent an integer of 4 to 12
  • x and y each independently represent 0 or 1
  • a reference symbol "*" and a reference symbol "**" respectively represent the binding sites to a silicon
  • a method for manufacturing a charging member in which the polymer compound is a cross-linked product of a hydrolyzed condensate of a hydrolyzable compound having a structure represented by the following general formula (12) and at least one of the hydrolyzed condensates of hydrolyzable compounds having structures represented by the following general formulas (13) to (16), comprising:
  • R 33 represents any one of the following general formulas (17) to (20) and R 34 to R 36 each independently represent an alkyl group having 1 to 4 carbon atoms.
  • R 37 to R 53 each independently represent an alkyl group having 1 to 9 carbon atoms.
  • R 54 to R 58 , R 59 to R 65 , R 66 , R 67 and R 72 , R 73 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a carboxyl group or an amino group
  • R 57 , R 58 , R 62 to R 65 , R 70 , R 71 and R 76 to R 79 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • n', m', l', q', s' and t' each independently represent an integer of 1 to 8
  • p' and r' each independently represent an integer of 4 to 12
  • a reference symbol "*" indicates a binding site with a silicon atom of the general formula (12).
  • a method for manufacturing a charging member in which the polymer compound is a cross-linked product of a hydrolyzed condensate of a hydrolyzable compound having a structure represented by the above general formula (12), at least one of the hydrolyzed condensates of hydrolyzable compounds having structures represented by the general formulas (13) to (16) and a hydrolyzed condensate of a hydrolyzable compound having a structure represented by the following general formula (21), comprising
  • R 80 represents an alkyl group having 1 to 21 carbon atoms or a phenyl group and R 81 to R 83 each independently represent an alkyl group having 1 to 4 carbon atoms.
  • the number of points in contact with a photosensitive member is limited to thereby reduce a contact area with the photosensitive member. Owing to this, adhesion of a toner and external additives is suppressed even if it is used for a long time, enabling to provide a surface rarely contaminated with dirt. As a result, a charging member capable of maintaining uniform charge for a long time can be obtained.
  • FIG. 2 shows a section of a charging member according to an embodiment of the present invention.
  • the charging member has a supporting member 101, a conductive elastic layer 102 and a surface layer 103.
  • FIG. 1 is an enlarged sectional view of a region nearby the surface of the charging member.
  • the charging member has cracks 104 developing from the surface and reaching the elastic layer 102.
  • the cracks 104 have edge portions 105 convexly raised. Owing to the raised edge portions 105, the surface of the charging member is roughened.
  • FIG. 5A is a top view of the surface of the charging member (binarized) and FIG. 5B is a bird's eye view thereof. From FIG. 5A , it is found that countless cracks 104 are present in the surface of the charging member. Furthermore, from FIG. 5B , it is found that the edge portions 105 of the cracks 104 are convexly raised.
  • FIG. 6A shows the shape of the cracks 104 present in the surface of the charging member.
  • FIG. 6B shows the convexoconcave states of the surface along with lines 1 to 5 in FIG. 6A .
  • the transverse axis shows the state along with the line ( ⁇ m), whereas the vertical axis shows the state along with the depth direction ( ⁇ m).
  • the thickness of the surface layer is 2 ⁇ m.
  • cracks have a depth of several ⁇ m and are developed up to the elastic layer.
  • a supporting member having conductivity As the supporting member, a supporting member having conductivity is used. Specific examples are as follows: supporting members formed of a metal (or a metal alloy) of iron, copper, stainless steel, aluminum, aluminum alloy or nickel.
  • one or two or more elastic materials such as rubber conventionally used in elastic layers (conductive elastic layers) of charging members can be used.
  • the rubber are as follows: urethane rubber, silicone rubber, butadiene rubber, isoprene rubber, chloroprene rubber, styrene-butadiene rubber, ethylenepropylene rubber, polynorbornene rubber, styrene-butadienestyrene rubber, acrylonitrile rubber, epichlorohydrin rubber and alkyl ether rubber.
  • the conductivity of the conductive elastic layer can be set to be a predetermined value by appropriately using a conductant agent in the conductive elastic layer.
  • the electrical resistivity of the conductive elastic layer can be controlled by appropriately selecting the type and use amount of a conductant agent.
  • the electrical resistivity favorably falls within the range of 10 2 to 10 8 ⁇ , and more favorably within the range of 10 3 to 10 6 ⁇ .
  • conductive carbons such as Ketjen black EC, acetylene black, carbon for rubber, oxidized carbon for color (ink) and thermolytic carbon can be used.
  • graphite such as naturally occurring graphite and man-made graphite can be used.
  • an inorganic or organic filler and crosslinking agent may be added.
  • the hardness of the conductive elastic layer is favorably 60° or more and 85° or less and particularly favorably 70° or more and 80° or less in terms of MD-1, in view of suppressing deformation of the charging member when the charging member is brought into contact with a photosensitive member, which is a member to be charged.
  • MD-1 falls within the above range, the depth of cracks in the conductive elastic layer can be easily controlled by use of cure shrinkage of the coating film.
  • a desired surface roughness (Rz) of the conductive elastic layer is favorably 3.0 ⁇ m or more and 12.0 ⁇ m or less and particularly favorably 5.0 or more and 10.0 ⁇ m or less.
  • the conductive elastic layer is formed on a supporting member by blending raw materials for the conductive elastic layer by an air-tight mixer, etc. and molding it by a known method such as extrusion molding, injection molding or compression molding. Note that, the conductive elastic layer is, if necessary, adhered on the supporting member via an adhesive.
  • the conductive elastic layer formed on the supporting member is vulcanized as needed. If a vulcanization temperature is rapidly raised, volatile by-products such as a vulcanization accelerator are gasified through a vulcanization reaction to form voids. Accordingly, a heating zone is favorably partitioned into two zones. A first zone is maintained at a temperature lower than the vulcanization temperature to release a gas component and thereafter vulcanization is performed in a second zone.
  • the surface layer contains a polymer compound having a Si-O-M bond and the polymer compound contains at least one of the structural units represented by the following general formula (1) and the general formula (2) and at least one of the structural units represented by the following general formula (3).
  • M represents an element selected from the group consisting of Ti, Zr and Hf.
  • General formula (2) MO 5/2 represents an element selected from the group consisting of Ti, Zr and Hf.
  • M represents an element Ta.
  • R 1 and R 2 each independently represent any one of the following general formulas (4) to (7).
  • R 3 to R 7 , R 10 to R 14 , R 19 , R 20 , R 25 and R 26 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a carboxyl group or an amino group
  • R 8 , R 9 , R 15 to R 18 , R 23 , R 24 and R 29 to R 32 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 21 , R 22 , R 27 and R 28 each independently represent a hydrogen atom, an alkoxyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms
  • n, m, l, q, s and t each independently represent an integer of 1 to 8
  • p and r each independently represent an integer of 4 to 12
  • x and y each independently represent 0 or 1
  • a reference symbol "*" and a reference symbol "**" respectively represent the binding sites to a silicon
  • An example of the polymer compound according to the present invention has a structure, which is represented by the formula (3) wherein R 1 is represented by the formula (4) and R 2 is represented by the formula (5) and has a Si-O-Ti bond in a molecule.
  • the structure of the polymer compound is partly shown in Figure 10A .
  • another example of the polymer compound according to the present invention has a structure, which is represented by the formula (3) wherein R 1 is represented by the formula (4) and R 2 is represented by the formula (7) and has a Si-O-Ti bond in a molecule.
  • the structure of the polymer compound is partly shown in Figure 10B .
  • R 1 and R 2 of the above general formula (3) are represented by any of the following general formulas (8) to (11).
  • the Modulus of elasticity of the surface layer can be controlled or membrane characteristics of the surface layer, e.g., brittleness and flexibility, can be controlled.
  • adhesion of the elastic layer to the surface layer is improved depending upon the structure of the organic chain, particularly, if an ether site is present.
  • N, M, L, Q, S and T each independently represent an integer of 1 to 8, and x' and y' each independently represent 0 or 1. Furthermore, a reference symbol "*" and a reference symbol "**" respectively represent binding sites to a silicon atom and an oxygen atom of the general formula (3).
  • the atomic-number ratio of M to silicon is favorably 0.10 to 12.50 and more favorably 0.50 to 10.00. If the value is 0.10 or more, cracks are easily produced by cure shrinkage, producing a surface roughening effect. In contrast, if the value is 12.50 or less, storage stability of the resultant condensate and a dilution solution thereof is ensured.
  • the above polymer compound is a charging material being a cross-linked product of a hydrolyzed condensate of a hydrolyzable compound having a structure represented by the following general formula (12) and at least one of the hydrolyzed condensates of hydrolyzable compounds having structures represented by the general formulas (13) to (16). More specifically, since the hydrolyzed condensate is significantly shrunken in crosslinking, cracks are generated in the surface layer formed of the cross-linked product. In addition, adhesion property of the hydrolyzed condensate to the elastic layer is extremely high.
  • R 33 represents any one of the following general formulas (17) to (20) and R 34 to R 36 each independently represent an alkyl group having 1 to 4 carbon atoms. Furthermore, in the general formulas (13) to (16), R 37 to R 53 each independently represent an alkyl group having 1 to 9 carbon atoms.
  • R 54 to R 58 , R 59 to R 65 , R 66 , R 67 , R 72 and R 73 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxy group, a carboxyl group or an amino group
  • R 57 , R 58 , R 62 to R 65 , R 70 , R 71 and R 76 to R 79 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • n', m', l', q', s' and t' each independently represent an integer of 1 to 8
  • p' and r' each independently represent an integer of 4 to 12
  • a reference symbol "*" represents a binding site with a silicon atom of the general formula (12).
  • hydrolyzable titanium compound having a structure represented by the general formula (13) will be described below.
  • a hydrolyzable tantalum compound having a structure represented by the general formula (16) will be described below.
  • (16-1) tantalum methoxide
  • (16-2) tantalum ethoxide
  • (16-3) tantalum n-propoxide
  • (16-4) tantalum i-propoxide
  • (16-5) tantalum n-butoxide
  • (16-6) tantalum t-butoxide
  • (16-7) tantalum 2-ethylhexoxide
  • hydrolyzable silane compound having a structure represented by the general formula (18) will be described below.
  • hydrolyzable silane compound having a structure represented by the general formula (20) will be described below.
  • the polymer compound is a cross-linked product of a hydrolyzed condensate of a hydrolyzable compound having a structure represented by the general formula (12), at least one of the hydrolyzed condensates of hydrolyzable compounds having structures represented by the general formulas (13) to (16) and a hydrolyzed condensate of a hydrolyzable compound having a structure represented by the following general formula (21).
  • a cross-linked product can form cracks of the present invention by cure shrinkage during the production process of the cross-linked product.
  • the material composition of the surface of the charging member can be constituted of a single system containing no filler. Furthermore, the film thickness of the surface layer can be reduced.
  • General formula (21) R 80 -Si (OR 81 ) (OR 82 ) (OR 83 )
  • R 80 represents an alkyl group having 1 to 21 carbon atoms or a phenyl group
  • R 81 to R 83 each independently represent an alkyl group having 1 to 4 carbon atoms.
  • hydrolyzable silane compound having a structure represented by the general formula (21) will be described below.
  • hydrolyzable silane compound having a structure represented by the general formula (21) it is favorable that a hydrolyzable silane compound wherein R 80 is a straight alkyl group having 6 to 10 carbon atoms is used in combination with a hydrolyzable silane compound wherein R 80 is a phenyl group. In this case, even if a monomer structure is changed by a hydrolyzed and condensation reaction, compatibility to a solvent is satisfactory.
  • metal element M any element selected from the group consisting of Ti, Zr, Hf and Ta is used.
  • M/Si 2.0
  • difference in reaction rate or number of valences depending upon the type of M presumably reflects.
  • the Modulus of elasticity tends to increase.
  • film (surface layer) density is determined by the size of microparticles and directly influences the Modulus of elasticity of the film.
  • the degree of cure shrinkage of the coating film increases. It is found that the size of microparticles directly influences surface cracks, i.e., cure shrinkage, and influences the raising degree of convex-form edge portions of cracks.
  • a desired film-thickness of the surface layer is 0.10 to 2.50 ⁇ m, particularly 0.15 to 2.00 ⁇ m. This is because cracks can be easily developed from the surface layer to the elastic layer by cure shrinkage of a coating film formed of a coating material for forming a surface layer. As a result, the effect of convexly raising edge portions of cracks increases. This is advantageous in roughening the surface. Furthermore, a desired volume resistivity of the surface layer is 10 10 to 10 16 ⁇ cm.
  • the charging member of the present invention has a crack developed by cure shrinkage of a coating film, and the crack extends from the surface of the surface layer to the elastic layer.
  • the edge portion of the crack is convexly raised, thereby roughening the surface of the charging member.
  • the size of the crack can be expressed by surface roughness (Rz) and the depth (Ry) of the crack.
  • the height of convex edge portion of the crack is favorably about 0.5 ⁇ m or more and 35.0 ⁇ m or less.
  • the surface roughness (Rz) of the charging member is favorably 5 ⁇ m or more and 25 ⁇ m or less, particularly favorably 7 ⁇ m or more and 22 ⁇ m or less and further favorably 10 ⁇ m or more and 20 ⁇ m or less.
  • the depth (Ry) of the crack of the charging member refers to the distance between the maximum height of the crack edge portion (convex portion) of the surface layer and the maximum depth of the crack developed after cure shrinkage, extending to the conductive elastic layer.
  • the depth (Ry) of the crack in the surface of the charging member is inevitably larger than the depth of the crack from the surface of the conductive elastic layer, by the maximum height of the edge portions (convex portion) of the surface layer, which is included in Ry.
  • the charging member according to the present invention can be manufactured, for example, by a method including the following steps (1) to (3).
  • a solution mixture which contains a hydrolyzable silane compound represented by the general formula (12) and at least one element selected from the group consisting of the hydrolyzable compounds represented by the general formulas (13) to (16), an optional hydrolyzable silane compound represented by the general formula (21), water and an alcohol, is heated and refluxed to hydrolyze and condense hydrolyzable compounds in the solution mixture to obtain a liquid-state condensate.
  • First stage reaction a hydrolyzable silane compound represented by the general formula (12) or hydrolyzable silane compounds represented by the general formula (12) and the general formula (21) are heated to reflux in the presence of water and an alcohol to perform hydrolyzed and condensation, thereby obtaining an intermediate condensate containing a hydrolyzed condensate of the hydrolyzable silane compound.
  • the second stage reaction the intermediate condensate and at least one hydrolyzable compound selected from the group of compounds having structures represented by the general formulas (13) to (16) are heated to reflux in the presence of water and an alcohol to perform hydrolyzed and condensation, thereby obtaining a final condensate.
  • the ratio WR (molar ratio) of water addition amount to hydrolyzable silane compounds in synthesizing a hydrolyzed condensate is favorably 0.3 or more and 6.0 or less.
  • WR water / hydrolyzable compound 12 + hydrolysable compound 21
  • the WR value is favorably 1.2 or more and 3.0 or less. As long as the water addition amount falls within the range, the degree of condensation during synthesis is easily controlled. Furthermore, the condensation rate is easily controlled and the storage stability of a hydrolyzed condensate or a diluted solution thereof is effectively improved. Furthermore, it is favorable that the WR value falls within the range. This is because, if so, synthesis can be performed within the range of pH where the epoxy group of the above general formula (12) is not opened.
  • the alcohol to be used in synthesizing a condensate it is favorable to use a primary alcohol alone, a mixture of a primary alcohol and a secondary alcohol, or a mixture of a primary alcohol and a tertiary alcohol. Particularly, a combination of ethanol, methanol and 2-butanol and a combination of ethanol and 2-butanol are favorable.
  • a photopolymerization initiator is added to the condensate obtained in step (1) and if necessary, a solvent is added to appropriately adjust a solid substance concentration to prepare a coating material for forming a surface layer.
  • a solvent in view of volatility may be used other than the solvent used in synthesis, in order to improve the coating property of a coating material.
  • the appropriate solvent include 2-butanol, ethyl acetate, methylethyl ketone or a mixture thereof.
  • a cationic polymerization catalyst serving as a photopolymerization initiator is favorably added to a coating material.
  • the epoxy group shows high reactivity to an onium salt of a Lewis acid activated by an activation energy beam
  • an onium salt of a Lewis acid is favorably used as a cationic polymerization catalyst.
  • cationic polymerization catalysts for example, a borate salt, a compound having an imide structure, a compound having a triazine structure, an azo compound and a peroxide are mentioned.
  • a borate salt a compound having an imide structure, a compound having a triazine structure, an azo compound and a peroxide are mentioned.
  • an aromatic sulfonium salt and an aromatic iodonium salt are favorable.
  • a bis(4-tert-butylphenyl)iodonium salt a compound having a structure represented by the following chemical formula (22) (trade name: Adeka Optomer-SP150, manufactured by ADEKA Corporation) and a compound having a structure represented by the following chemical formula (23) (trade name: IRGACURE 261, manufactured by Ciba Specialty Chemicals Inc.) are favorable.
  • the addition amount of cationic polymerization catalyst serving as a photopolymerization initiator is favorably 1.0 to 3.0 parts by mass relative to the solid substance of a hydrolyzed condensate (100 parts by mass). As long as the addition amount falls within the range, curing characteristics and the solubility of the photopolymerization initiator are satisfactory.
  • the coating material prepared in the step (2) is applied on the conductive elastic layer formed on a substrate to form a coating film of the coating material.
  • a known method such as coating using a roll coater, dip coating and ring coating can be used.
  • a cationic polymerizable group contained in a molecule of a condensate of the coating film on the conductive elastic layer is allowed to react, thereby crosslinking the condensate to obtain the polymer compound according to the present invention.
  • an epoxy group contained in a molecule of a condensate is cleaved to form a polymer compound.
  • a crosslinking method a method of applying an activation energy beam and a heating method are mentioned. Consequently, a condensate is crosslinked and the coating film is cured, constituting a surface layer.
  • the activation energy beams UV ray is favorable.
  • the cumulative light amount of UV ray can be controlled by irradiation time, lamp output and the distance between an irradiation lamp and the material to be irradiated. Furthermore, the cumulative light amount may be gradually increased or decreased within the irradiation time.
  • UV-ray cumulative light amount meter (trade name: UIT-150-A, UVD-S254, both are manufactured by Ushio Inc.). Furthermore, in the case of using an excimer UV lamp, UV-ray cumulative light amount can be measured by a UV-ray cumulative light amount meter (trade name: UIT-150-A, VUV-S172, both are manufactured by Ushio Inc.).
  • a condensate which is obtained by hydrolyzing 3-glycidoxypropyltrimethoxysilane serving as a compound represented by the above general formula (12) and at least one hydrolyzable compound selected from the group consisting of those represented by the above general formulas (13) to (16), has an epoxy group as a cationic polymerizable group.
  • a condensate since an epoxy ring is opened in the presence of a cationic polymerization catalyst (expressed by R + X - in FIG. 9 ), polymerization consequently proceeds in a chain-reaction manner.
  • polysiloxanes containing MO 4/2 or MO 5/2 are mutually crosslinked and cured to form a polymer compound according to the present invention.
  • n is an integer of 1 or more.
  • FIG. 3 shows a schematic structure of an electrophotographic apparatus provided with a process cartridge having the charging member of the present invention.
  • the electrophotographic apparatus has a cylindrical photosensitive member 1, which is rotatory driven at a predetermined circumferential speed about a shaft 2 in the direction indicated by the arrow.
  • the photosensitive member may have a supporting member and a photosensitive layer, a charge injection layer, a surface layer, etc. formed on the supporting member.
  • the surface of the photosensitive member rotatory driven is uniformly charged positively or negatively to a predetermined potential by a charging member 3, and subsequently irradiated with exposure light (image exposure light) 4 emitted from a light exposure unit (not shown in the figure) such as a slit light exposure unit or a laser beam scanning light exposure unit to form an electrostatic latent image corresponding to a desired image.
  • a light exposure unit not shown in the figure
  • a direct voltage or a voltage obtained by superimposing an alternate-current voltage to a direct-current voltage is applied to the charging member 3 by a voltage application unit (not shown in the figure).
  • the electrostatic latent image formed on the surface of the photosensitive member 1 is formed into a toner image by supplying a developer to the latent image by a develop roller provided in a developing unit 5 through reversal development or normal development.
  • the toner image on the surface of the photosensitive member 1 is sequentially transferred onto a transfer material P such as a paper sheet, which is fed to the space between the photosensitive member 1 and a transfer roller 6 in synchronisms with the rotation of the photosensitive member, by a transfer bias applied to the transfer roller 6.
  • a transfer material P such as a paper sheet
  • the developing unit for example, a jumping developing unit, a contact developing unit and a magnetic brushing unit are mentioned.
  • a roller having an elastic layer controlled to have a medium resistivity and formed on a supporting member can be used.
  • the transfer material P having a toner image transferred thereon is separated from the surface of the photosensitive member 1 and introduced into a fixing unit 8, in which the toner image is fixed, and output from the apparatus as an image formed matter (printed matter, copy).
  • the image formed matter is introduced into a recirculation feeding mechanism and introduced again to a transfer section.
  • the developer (toner) that remains unused in a transfer process is removed by a cleaning unit 7 such as a cleaning blade.
  • a cleaning unit 7 such as a cleaning blade.
  • the surface of the photosensitive member 1 is cleaned and further discharged by pre-exposure light emitted from a pre-light exposure unit and then repeatedly used for image formation.
  • the charging unit is a contact charging unit, the pre-light exposure is not necessarily used.
  • the photosensitive member 1, charging member 3, developing unit 5 and cleaning unit 7 are integrated in the form of a process cartridge 9, which is detachably attached to an electrophotographic apparatus main body by use of a guiding unit 10 such as a rail.
  • Members other than the aforementioned members, i.e., members appropriately selected from those of a transfer unit are integrated in a cartridge, which can be detachably attached to the electrophotographic apparatus main body.
  • FIG. 4 shows a schematic sectional view of the developing apparatus serving as the developing unit 5.
  • an electrographic photosensitive drum 501 which serves as an electrostatic latent image holder for holding an electrostatic latent image formed by a known process, is rotated in the direction indicated by arrow B.
  • a developing sleeve 508 serving as a developer carrier holds a one-component developer 504 having a magnetic toner, which is supplied by a hopper 503 serving as a developer container and is rotated in the direction indicated by arrow A.
  • the developer 504 is fed to a developing region D at which the developing sleeve 508 faces the photosensitive member 501.
  • a magnet roller 505 housing magnets in contact therewith is arranged in order to magnetically attract and hold the developer 504 onto the developing sleeve 508.
  • a developing sleeve 508 used in the developing apparatus of the present invention has a metal cylindrical tube 506 as a substrate and a conductive-resin coating layer 507 formed on the tube by coating.
  • a stirring vane 510 is provided for stirring the developer 504.
  • Reference numeral 513 represents a gap, which means that the developing sleeve 508 and the magnet roller 505 are arranged in non-contact with each other.
  • the developer 504 is triboelectrically charged due to friction between magnetic toner particles constituting the developer and friction with the conductive-resin coating layer 507 formed on the developing sleeve 508, such that an electrostatic latent image on the photosensitive drum 501 can be developed.
  • a magnetic regulation blade 502 formed of a ferromagnetic metal is provided as a developer-thickness regulation member in order to regulate the thickness of the developer 504 to be fed to the developing region D.
  • the magnetic regulation blade 502 is suspended from the hopper 503 so as to face the surface of the developing sleeve 508 with a gap of about 50 to 500 ⁇ m in width interposed between them. Since magnetic lines from a magnetic pole N1 of the magnet roller 505 are converged on the magnetic regulation blade 502, a thin layer of the developer 504 is formed on the developing sleeve 508.
  • the developer (toner) used in the present invention favorably has a mass average particle size within the range of 4 ⁇ m or more and 11 ⁇ m or less. If such a developer (toner) is used, the charge amount of toner or image quality and image density, etc., are well balanced.
  • the binder resin for a developer (toner) resins generally known in the art can be used. Examples thereof include a vinyl resin, a polyester resin, a polyurethane resin, an epoxy resin and a phenol resin. Of them, a vinyl resin and a polyester resin are favorable.
  • a charge control agent can be used in combination by adding it to a toner particle (internal addition) or by mixing it with toner particles (external addition), in order to improve charge properties. This is because a charge amount can be optimally controlled in accordance with a developing system by the charge control agent.
  • Examples of a positive charge control agent include agents modified by nigrosine, a triaminotriphenylmethane dye and a fatty acid metal salt; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammoniumtetrafluoroborate; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide and dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate, and dicyclohexyltin borate. These can be used alone or in combination of two or more types.
  • an organic metal compound and a chelate compound are effective as a negative charge control agent.
  • examples thereof include aluminum acetylacetonate, iron (II) acetylacetonate and chromium 3,5-ditertiarybutylsalicylate.
  • an acetyl acetone metal complex, a mono-azo metal complex and a metal complex or salt of naphthoic acid or salicylic acid are favorable.
  • the developer (toner) is a magnetic developer (toner)
  • a magnetic material is blended.
  • the magnetic materials include metal oxides such as iron oxides including magnetite, maghemite and ferrite; magnetic metals such as Fe, Co, Ni; and alloys between these metals and a metal such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, and V, and a mixture of these.
  • the magnetic material may also serve as a colorant.
  • the colorant to be blended with the developer (toner) a pigment and a dye conventionally used in this field can be used, and appropriately selected in use.
  • a mold release agent is favorably blended.
  • the mold release agent include an aliphatic hydrocarbon wax such as a low molecular weight polyethylene, a low molecular weight polypropylene, microcrystalline wax and paraffin wax and wax containing, as a main component, a fatty acid ester such as carnauba wax, Fischer-Tropsch wax, Sasolwax and Montan wax.
  • an inorganic impalpable powder such as silica, titanium oxide and alumina is externally added to the developer (toner) in order to improve environmental stability, charge stability, developing property, flowability, storage stability and cleaning performance. More specifically, an inorganic impalpable powder is favorably present in the proximity of the developer surface. Of them, silica fine powder is favorable.
  • Components (1), (2-1), (3), (4) and (5) (the amounts thereof are shown in Table 1) were kneaded in a 6L kneader for 20 minutes and then components (6) and (7) (the amounts thereof are shown in Table 1) were added and kneaded in an open roll for further 8 minutes to obtain a kneaded product I.
  • thermosetting adhesive containing a metal and a rubber (trade name: Metalock N-33, manufactured by ToyoKagaku Kenkyusho Co., Ltd.) was applied and dried for 30 minutes at a temperature of 80°C, and thereafter, dried for further one hour at a temperature of 120°C.
  • kneaded product I was extruded concentrically in a cylindrical shape having an outer diameter of 8.75 to 8.90 mm onto the supporting member provided with the aforementioned adhesive layer and an edge portion was cut off to layer a conductive elastic layer unvulcanized (length: 242 mm) on the outer periphery of the supporting member.
  • the temperature conditions during the extrusion process were set as follows: head temperature: 90°C, cylinder temperature: 90°C, and screw temperature: 90°C.
  • the aforementioned roller was vulcanized by use of a communicating heating furnace having two zones set at different temperatures.
  • the roller was passed through the first zone set at a temperature of 80°C for 30 minutes and through the second zone set at a temperature of 160°C for 30 minutes.
  • the unvulcanized conductive elastic layer was vulcanized.
  • the edge portions of the vulcanized conductive elastic layer in the width direction were cut off and the length of the conductive elastic layer in the shaft direction was set to 232 mm. Furthermore, the surface of the conductive elastic layer was polished with a rotatory grind stone to form into a crown shape having an edge diameter of 8.26 mm, a middle diameter of 8.5 mm. This is designated as a conductive elastic roller 1.
  • Evaluation 1 Evaluation of conductive elastic layer
  • the surface of the conductive elastic layer of the conductive elastic roller 1 were evaluated for 10-point average roughness (Rz), maximum depth (Ry), hardness and deflection of outer-diameter difference.
  • the results are shown in Table 2.
  • the maximum depth Ry is measured as follows. From the roughness curve, a standard length is just excised out in the direction of the line indicating average roughness. In the portion excised out, the interval between a peak line and a valley-floor line is measured in the lengthwise magnification direction of the roughness curve.
  • the maximum depth Ry represents, in the standard measurement length, the distance between the maximum height of a crack edge portion (convex portion) and the maximum depth including cracks developed to the conductive elastic layer after cure shrinkage.
  • Ten-point average roughness (Rz) and the maximum depth (Ry) were measured in accordance with Japanese Industry standard (JIS) B0601 (1994). Measurement conditions used herein were as follows: an evaluation length: 8.0 mm, a cut off value: 0.8mm, a feed rate: 0.5 mm/s, a filter characteristic: 2CR.
  • Hardness was measured by a micro rubber hardness meter (MD-1 capa, manufactured by Kobunshi Keiki Co., Ltd.). Furthermore, deflection was measured by high-precision laser measuring machine, LSM-430v, manufactured by Mitutoyo Corporation. To be more specific, the outer diameter was measured by the measuring machine and the difference between the maximum outer diameter and the minimum outer diameter was determined as an outer-diameter difference. The measurement was performed at 5 points and the average value of the outer-diameter difference of the 5 points was determined as a deflection of the measured material.
  • a conductive elastic roller 2 and conductive elastic roller 3 were obtained in the same manner as in the conductive elastic roller 1 except that the surface polishing conditions of vulcanized conductive elastic layer were changed.
  • conductive elastic roller was obtained in the same manner as in the conductive elastic roller 1 except that a component (2-2) was used in the amount shown in Table 1 in place of the component (2-1).
  • a conductive elastic roller 4, and a conductive elastic roller 5 were obtained in the same manner as in the conductive elastic roller 3 except that the surface polishing conditions of the vulcanized conductive elastic layer of the aforementioned conductive elastic roller were changed.
  • conductive elastic roller 6 and conductive elastic roller 7 were obtained in the same manner as in conductive elastic roller 1 except that a component (2-3) was used in the amount shown in Table 1 in place of the component (2-1) and the surface polishing conditions of the vulcanized conductive elastic layer were changed. These conductive elastic rollers 2 to 7 were evaluated in the same manner as in conductive elastic roller 1. The evaluation results of conductive elastic rollers 1 to 7 are shown in Table 2 below. Table 2 Conductive elastic roller No.
  • Table 3 3-Glycidoxypropyltrimethoxysilane (EP-1) [trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.] 11.56g (0.049 mol) Hexyltrimethoxysilane (He) [trade name: KBM-3063, manufactured by Shin-Etsu Chemical Co., Ltd.] 62.11 g (0.301 mol) Ethanol (EtOH), [special grade, Kishida Chemical Co., Ltd.] 91.87 g
  • Evaluation (1) Evaluation of storage stability of condensate 1 dilution solution
  • condensate 1 was diluted with ethanol to control the content of a solid substance to be 1.3 mass %. In this manner, a dilution solution of condensate 1 was obtained.
  • the storage stability of the resultant condensate 1 dilution solution was evaluated based on the following criteria.
  • Evaluation (2) Evaluation of chemical structure of a condensate hardened material
  • a hardened material of condensate 1 prepared in the following manner was subjected to measurement by a nuclear magnetic resonance apparatus (trade name: JMN-EX400, manufactured by JEOL) to measure 29 Si-NMR and 13 C-NMR spectra. In this manner, it was confirmed that a structure represented by the general formula (3) is present in the hardened material.
  • an aromatic sulfonium salt [trade name: Adeka optomer SP-150, manufactured by ADEKA Corporation] serving as a photo cation polymerization initiator was diluted with methanol to 10 mass %. Then, the dilution solution of the photo cation polymerization initiator was added such that the liquid amount of the photo cation polymerization initiator is brought to be 3.0 parts by mass based on the solid substance (100 parts by mass) of a condensate 1 dilution solution prepared in the same manner as described in evaluation (1). To this, a solvent in which ethanol and 2-butanol were mixed in a ratio of 1:1 (mass ratio) was added to control a theoretical solid substance concentration to be 7.0 mass %. This was designated as coating liquid 1.
  • spin-coat apparatus 1H-D7 (trade name: manufactured by Mikasa Co., Ltd.). Spin-coat conditions were set as follows: rotation rate: 300 rpm, a rotation time: 2 seconds.
  • the coating film of coating liquid 1 was dried and irradiated with UV ray having a wavelength of 254 nm to cure the coating film.
  • the cumulative light amount of UV ray applied to the coating film was set to 9000 mJ/cm 2 .
  • UV ray was applied by use of a low-pressure mercury lamp (manufactured by Harison Toshiba Lighting Corporation).
  • the cured film was removed from the aluminum sheet, and ground by a mortar made of agate to prepare a sample for NMR measurement.
  • the sample was subjected to measurement by a nuclear magnetic resonance apparatus (trade name: JMN-EX400, manufactured by JEOL) to measure 29 Si-NMR spectrum and 13 C-NMR spectrum.
  • Condensate intermediates 2 to 7 were prepared in the same manner as in condensate intermediate 1 except that the compositions shown in Table 5 below were employed. Note that the compounds represented by brevity codes (EP-1 to EP-5, He, Ph) in Table 5 are more specifically shown in Table 11. Table 5 Condensate intermediate No.
  • Condensates 2 to 60 were prepared in the same manner as in condensate 1 except that the compositions shown in Tables 6 to 9 below were employed and subjected to evaluation (1) and evaluation (2). The evaluation results are collectively shown in Tables 6 to 9. Note that the compounds represented by brevity codes (Tr-1 to Tr-3, Zr-1 to Zr-3, Hf-1 to Hf-3 and Ta-1 to Ta-3) shown in Tables 6 to 9 are more specifically shown in Table 11. Table 6 Condensate No. Condensate intermediate Compound of Formula (13) Ti/Si Evaluation (1) Evaluation (2) No.
  • Condensate intermediate 4 was formed into condensate 61, which was subjected to the evaluation (1) and evaluation (2). The results are shown in Table 10.
  • Condensates 62 to 65 were prepared in the same manner as condensate intermediate 1 except that the compositions of Table 10 below were employed and subjected to the evaluation (1). The results are shown in Table 10. Note that condensates 62 to 65, since white turbidity and precipitation were produced during synthesis, failed to prepare coating solutions to be subjected to the evaluation (2). Therefore, evaluation (2) was not performed. Table 10 Condensate No.
  • EP-2 4-(Trimethoxysilyl)bu tane-1,2-epoxide Carbone Scientific
  • EP-3 4-(Trimethoxysilyl) bu tane-1,2-epoxide SiKÉMIA
  • EP-4 2-(3,4-Epoxycycloh exyl) ethyltrimetho xysilane Shin-Etsu Chemical Co., Ltd. He Hexyltrimethoxysilane H 3 C-(CH 2 ) 5 -Si(OMe) 3 Shin-Etsu Chemical co., Ltd. Ph Shin-Etsu Chemical Co., Ltd. Ti-1 Titanium i-propoxide Ti-(OiPr) 4 Kojundo Chemical Laboratory Co., Ltd.
  • Example 1 Preparation of charging rollers 1-1 to 1-3
  • Three conductive elastic rollers 1 were prepared in the above [1].
  • coating materials No.1-1 to 1-3 were applied, respectively, by ring coating (ejection amount: 0.120 ml/s, speed of a ring portion: 85 mm/s, total ejection amount: 0.130 ml).
  • UV ray having a wavelength of 254 nm was applied such that the cumulative light amount reached 9000 mJ/cm 2 . In this manner, condensate 1 of the coating material was crosslinked to form a surface layer.
  • Evaluation (3) Evaluation of coating property of coating material for forming a surface layer Appearance of the surface of a charging roller was visually observed to evaluate the coating property of a coating material for forming a surface layer based on the following criteria.
  • a cured film of condensate 1, 5.0 ⁇ m in thickness was formed in the same manner as in Evaluation (2).
  • the cured film was subjected to a surface film physical property test (trade name: Fischer scope H 100 V; manufactured by Fischer Instruments K. K.), in which an indenter was allowed to invade into the surface of the object to be measured at a rate of 0.5 ⁇ m/7s. The value at this time was determined as Modulus of elasticity.
  • each charging roller was observed by use of a color 3D laser microscope (trade name: VK-8700 manufactured by Keyence Corporation) at a magnification ratio of 1000 times (objective lens 50 times). Furthermore, surface roughness (Rzjis, Ry) was calculated by use of analysis software, VK Analyzer.
  • the detected O1s spectrum was separated into peaks corresponding to binding modes (Ti-O-Ti binding, Si-O-Ti binding, Si-O-Si binding) (see FIG. 8 ). Owing to the presence of these peaks, the chemical bindings were confirmed to be present in a surface layer.
  • each of the charging rollers and an electrographic photosensitive member were integrally supported and installed in a process cartridge (trade name: "HP 35A (CB435A)", manufactured by HP).
  • the process cartridge was fitted to a laser beam printer for outputting a A4 size paper sheet with a longitudinal side as a leading edge (trade name: "HP LaserJet P1006 Printer”, manufactured by HP).
  • the print speed of the laser beam printer is 17 sheets/minute and an image resolution is 600 dpi.
  • the electrographic photosensitive member installed together with a charging roller in the process cartridge is an organic electrographic photosensitive member obtained by forming an organic photosensitive layer of 8.0 ⁇ m in thickness on a supporting member.
  • the organic photosensitive layer is a laminate-type photosensitive layer obtained by stacking a charge generation layer and a charge transport layer containing a polycarbonate (a binder resin) in the order from the supporting member.
  • the charge transport layer serves as a surface layer of the electrographic photosensitive member.
  • the developer (toner) used in the laser beam printer is a mixture of a colorant, a charge control agent, a mold release agent, an inorganic microparticle, etc. added to a binder resin for a developer.
  • the types of developers there are a magnetic one-component type developer essentially containing a magnetic material and a non-magnetic one-component type developer containing no magnetic material.
  • the type of developer is appropriately selected depending upon the developing apparatus.
  • a magnetic one-component developer was used.
  • An image used herein was formed, on an A4 size paper, by drawing horizontal lines of two dots in width, which is perpendicular to the rotation direction of an electrographic photosensitive member, at the intervals of 118 spaces. Furthermore, output was performed under a 25°C/55%RH environment. Image was formed in a so-called intermittent mode in which rotation of an electrographic photosensitive member is stopped for 7 seconds every time a single paper sheet was printed. In this manner, the image forming operation was performed over two days at an output rate of 1000-image sheets per day. In total, 2000-electrographic image sheets were output. The half tone images thus formed were visually observed for the presence or absence of a transverse streak due to charge failure and the degree thereof, and evaluation was performed based on the following criteria.
  • Coating materials 2-1 to 2-3, 3-1 to 3-3 for forming a surface layer were prepared in the same manner as in coating materials 1-1 to 1-3 except that condensate 2 was used.
  • Charging rollers 2-1 to 2-3, 3-1 to 3-3, 4-1 to 4-4, 5-1 to 5-2, 6-1 to 6-3, 7 to 14 were prepared in the same manner as in Example 1 except that the above coating materials were used, and then subjected to evaluations (3) to (8).
  • Charging rollers 15-1 to 15-6 were prepared in the same manner as in charging roller 1 except that coating material No. 15 was used and conductive rollers 2 to 7 were used in place of the conductive elastic roller 1, and subjected to evaluations (3) to (8).
  • Coating materials 16-1 to 16-3, 17-1 to 17-3, 18-1 to 18-3 for forming a surface layer were prepared in the same manner as in coating materials 1-1 to 1-3 except that condensates 16 to 18 were used.
  • Charging rollers 16-1 to 16-3, 17-1 to 17-3, 18-1 to 18-3, 19-1 to 19-3, 20-1 to 20-2, 21-1 to 21-3, 22 to 29 were prepared in the same manner as in Example 1 except that the above coating materials were used, and then subjected to evaluations (3) to (8).
  • Charging rollers 30-1 to 30-6 were prepared in the same manner as in charging roller 1 except that coating material No. 30 was used and conductive rollers 2 to 7 were used in place of the conductive elastic roller 1 and then subjected to evaluations (3) to (8).
  • Coating materials 31-1 to 31-3, 32-1 to 32-3, 33-1 to 33-3 for forming a surface layer were prepared in the same manner as in coating materials 1-1 to 1-3 except that condensates 31 to 33 were used.
  • Charging rollers 31-1 to 31-3, 32-1 to 32-3, 33-1 to 33-3, 34-1 to 34-3, 35-1 to 35-2, 36-1 to 36-3, 37 to 44 were prepared in the same manner as in Example 1 except that the above coating materials were used and subjected to evaluations (3) to (8).
  • Charging rollers 45-1 to 45-6 were prepared in the same manner as in charging roller 1 except that coating material No. 45 was used and conductive rollers 2 to 7 were used in place of the conductive elastic roller 1 and subjected to evaluations (3) to (8).
  • Coating materials 46-1 to 46-3, 47-1 to 47-3, 48-1 to 48-3 for forming a surface layer were prepared in the same manner as in coating materials 1-1 to 1-3 except that condensates 46 to 48 were used.
  • Charging rollers 46-1 to 46-3, 47-1 to 47-3, 48-1 to 48-3, 49-1 to 49-3, 50-1 to 50-2, 51-1 to 51-3, 52 to 59 were prepared in the same manner as in Example 1 except that the above coating materials were used, and then subjected to evaluations (3) to (8).
  • Charging rollers 60-1 to 60-6 were prepared in the same manner as in charging roller 1 except that coating material No. 60 was used and conductive rollers 2 to 7 were used in place of the conductive elastic roller 1 and then subjected to evaluations (3) to (8).
  • Coating materials 61-1 to 61-3 for forming a surface layer were prepared in the same manner as in coating materials 1-1 to 1-3 except that condensate 61 was used.
  • Charging rollers 61-1 to 61-3 were prepared in the same manner as in Example 1 except that coating materials 61-1 to 61-3 were used, and then subjected to evaluations (3) to (8).

Claims (8)

  1. Ladungselement, das ein Trägerelement, eine elastische Schicht und eine Oberflächenschicht umfasst, wobei
    die Oberflächenschicht eine Polymerverbindung mit einer Si-O-M Bindung umfasst, und wobei die Polymerverbindung zumindest eine Struktureinheit aufweist, die aus Struktureinheiten ausgewählt ist, die unten durch eine allgemeine Formel (1) und eine allgemeine Formel (2) dargestellt sind, und eine Struktureinheit aufweist, die unten durch eine allgemeine Formel (3) dargestellt ist; und wobei
    das Ladungselement eine Spalte aufweist, die sich von dessen Oberfläche bis zu der elastischen Schicht erstreckt, und wobei die Spalte eine konvex ansteigende Kante aufweist, durch welche dessen Oberfläche aufgeraut ist:

            Allgemeine Formel (1)     MO4/2

    wobei M ein Element ausgewählt aus der Gruppe bestehend aus Ti, Zr und Hf darstellt;

            Allgemeine Formel (2)     MO5/2

    wobei M ein Element Ta darstellt;
    Figure imgb0053
     wobei R1 und R2 jeweils unabhängig eine aus den unteren allgemeinen Formeln (4) bis (7) darstellen;
    Figure imgb0054
    Figure imgb0055
    Figure imgb0056
    Figure imgb0057
    wobei R3 bis R7, R10 bis R14, R19, R20, R25 und R26 jeweils unabhängig ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen, eine Hydroxygruppe, eine Carboxylgruppe oder eine Aminogruppe darstellen;
    R8, R9, R15 bis R18, R23, R24 und R29 bis R32 jeweils unabhängig ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen darstellen; R21, R22, R27 und R28 jeweils unabhängig ein Wasserstoffatom, eine Alkoxylgruppe mit 1 bis 4 Kohlenstoffatomen oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen darstellen; n, m, I, q, s und t jeweils unabhängig eine ganze Zahl von 1 bis 8 darstellen; p und r jeweils unabhängig eine ganze Zahl von 4 bis 12 darstellen; x und y jeweils unabhängig 0 oder 1 darstellen; und ein Referenzsymbol "*" und ein Referenzsymbol "**"Bindungsstellen zu einem Siliciumatom bzw. einem Sauerstoffatom in der allgemeinen Formel (3) darstellen.
  2. Ladungselement nach Anspruch 1, wobei in der Polymerverbindung R1 und R2 von der allgemeinen Formel (3) jeweils unabhängig eine aus den unteren allgemeinen Formeln (8) bis (11) darstellen:
    Figure imgb0058
    Figure imgb0059
    Figure imgb0060
    Figure imgb0061
     wobei N, M, L, Q, S und T jeweils unabhängig eine ganze Zahl von 1 bis 8 darstellen; x' und y' jeweils unabhängig 0 oder 1 darstellen; und ein Referenzsymbol "*" und ein Referenzsymbol "*" Bindungsstellen zu einem Siliciumatom bzw. einem Sauerstoffatom in der allgemeinen Formel (3) darstellen.
  3. Ladungselement nach Anspruch 1 oder 2, wobei ein Atomanzahlverhältnis von M zu Silicium (M/Si) in der Polymerverbindung 0,10 bis 12,50 ist.
  4. Ladungselement nach einem der Ansprüche 1 bis 3, wobei die Polymerverbindung ein vernetztes Produkt eines hydrolysierten Kondensats einer hydrolysierbaren Verbindung mit einer durch die untere allgemeine Formel (12) dargestellten Struktur und zumindest einem aus hydrolysierten Kondensaten von hydrolysierbaren Verbindungen mit den durch die unteren allgemeinen Formeln (13) bis (16) dargestellten Strukturen ist:

            Allgemeine Formel (12):     R33-Si(OR34)(OR35)(OR36)

            Allgemeine Formel (13):     Ti(OR37)(OR38)(OR39)(OR40)

            Allgemeine Formel (14):     Zr(OR41)(OR42)(OR43)(OR44)

            Allgemeine Formel (15):     Hf(OR45)(OR46)(OR47)(OR48)

            Allgemeine Formel (16):     Ta(OR49)(OR50)(OR51)(OR52)(OR53)

    wobei R33 eine der unteren allgemeinen Formeln (17) bis (20) darstellt;
    R34 bis R36 jeweils unabhängig eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen darstellen; und R37 bis R53 jeweils unabhängig eine Alkylgruppe mit 1 bis 9 Kohlenstoffatomen darstellen;
    Figure imgb0062
    Figure imgb0063
    Figure imgb0064
    Figure imgb0065
    wobei R54 bis R58, R59 bis R65, R66, R67 und R72, R73 jeweils unabhängig ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen, eine Hydroxygruppe, eine Carboxylgruppe oder eine Aminogruppe darstellen;
    R57, R58, R62 bis R65, R70, R71 und R76 to R79 jeweils unabhängig ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen darstellen; n', m', I', q', s' und t' jeweils unabhängig eine ganze Zahl von 1 bis 8 darstellen; p' und r' jeweils unabhängig eine ganze Zahl von 4 bis 12 darstellen; und ein Referenzsymbol "*" eine Bindungsstelle mit einem Siliciumatom der allgemeinen Formel (12) indiziert.
  5. Ladungselement nach einem der Ansprüche 1 bis 3, wobei die Polymerverbindung ein vernetztes Produkt eines hydrolysierten Kondensats einer hydrolysierbaren Verbindung mit einer durch die allgemeine Formel (12) dargestellten Struktur, zumindest einem aus dem hydrolysierten Kondensaten von hydrolysierbaren Verbindungen mit den durch die allgemeinen Formeln (13) bis (16) dargestellten Strukturen, und eines hydrolysierten Kondensats einer hydrolysierbaren Verbindung mit einer durch die untere allgemeine Formel (21) dargestellten Struktur ist:

            allgemeine Formel (21):     R80-Si(OR81)(OR82)(OR83)

    wobei R80 eine Alkylgruppe mit 1 bis 21 Kohlenstoffatomen oder eine Phenylgruppe darstellt und R81 bis R83 jeweils unabhängig eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen darstellen.
  6. Verfahren zum Herstellen des Ladungselements nach Anspruch 4, das umfasst
    (i) Erhalten eines Flüssigzustandskondensats, das ein hydrolysiertes Kondensat einer hydrolysierbaren Verbindung mit einer durch die allgemeine Formel (12) dargestellten Struktur und zumindest einem aus den hydrolysierten Kondensaten von hydrolysierbaren Verbindungen mit durch die allgemeinen Formeln (13) bis (16) dargestellten Strukturen umfasst,
    (ii) Erhalten eines Beschichtungsmaterials zum Bilden einer Oberflächenschicht, das das Flüssigzustandskondensat und einen Photopolymerisationsinitiator umfasst, und
    (iii) Bilden eines Beschichtungsfilms aus dem Beschichtungsmaterial auf einer elastischen Schicht, die auf dem äußeren Umfang eines Trägerelements bereitgestellt ist, Vernetzen der hydrolisierten Kondensate durch Spalten einer Epoxidgruppe bei R33 des hydrolisierten Kondensats in dem Beschichtungsfilm und Bilden der Oberflächenschicht.
  7. Verfahren zum Herstellen des Ladungselements nach Anspruch 5, das umfasst
    (i) Erhalten eines Flüssigzustandskondensats, das ein hydrolysierbares Kondensat einer hydrolysierbaren Verbindung mit einer durch die obige allgemeine Formel (12) dargestellten Struktur, ein hydrolysiertes Kondensat einer hydrolysierbaren Verbindung mit einer durch die allgemeine Formel (21) dargestellten Struktur und zumindest einem aus den hydrolysierten Kondensaten von hydrolysierbaren Verbindungen mit den durch die allgemeine Formeln (13) bis (16) dargestellten Strukturen, umfasst,
    (ii) Erhalten eines Beschichtungsmaterials zum Bilden einer Oberflächenschicht, die das Flüssigzustandskondensat und einen Photopolymerisationsinitiator umfasst, und
    (iii) Bilden eines Beschichtungsfilms aus dem Beschichtungsmaterial auf einer elastischen Schicht, die auf dem äußeren Umfang eines Trägerelements bereitgestellt ist, Vernetzen einer Epoxidgruppe bei R33 des hydrolisierten Kondensats in dem Beschichtungsfilm, um den Beschichtungsfilm zu härten, und Bilden der Oberflächenschicht.
  8. Ladungselement nach Anspruch 4, wobei die hydrolysierbare Verbindung mit einer durch die allgemeine Formel (12) dargestellten Struktur eine hydrolisierbare Silanverbindung ist, die ausgewählt ist aus der Gruppe bestehend aus:
    (17-1): 4-(1,2-Epoxybutyl) trimethoxysilan,
    (17-2): 4-(1,2-Epoxybutyl) triethoxysilan,
    (17-3): 5,6-Epoxyhexyltrimethoxysilan,
    (17-4): 5,6-Epoxyhexyltriethoxysilan,
    (17-5): 8-Oxiran-2-yloctyltrimethoxysilan,
    (17-6): 8-Oxiran-2-yloctyltriethoxysilan,
    (18-1): Glycidoxypropyltrimethoxysilan,
    (18-2): Glycidoxypropyltriethoxysilan,
    (19-1): 2-(3,4-Epoxycyclohexyl) ethyltrimethoxysilan,
    (19-2): 2-(3,4-Epoxycyclohexyl) ethyltriethoxysilan,
    (20-1):3-(3,4-Epoxycyclohexyl) methyloxypropyltrimethoxysilan,
    (20-2):3-(3,4-Epoxycyclohexyl) methyloxypropyltriethoxysilan.
EP11829330.7A 2010-09-27 2011-09-22 Ladungselement und verfahren zur herstellung davon Not-in-force EP2624066B1 (de)

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JP4954344B2 (ja) 2012-06-13
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KR20130079547A (ko) 2013-07-10
CN103124931B (zh) 2015-06-17
CN103124931A (zh) 2013-05-29
JP2012113325A (ja) 2012-06-14
JP2012093720A (ja) 2012-05-17
KR101477941B1 (ko) 2014-12-30
US9372428B2 (en) 2016-06-21
EP2624066A4 (de) 2014-11-05

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